WO2021254892A1 - Carbonates de polyester obtenus à partir de diacides cycloaliphatiques, de 1,4 : 3,6-dianhydrohexitol et d'un autre composé dihydroxy aliphatique - Google Patents

Carbonates de polyester obtenus à partir de diacides cycloaliphatiques, de 1,4 : 3,6-dianhydrohexitol et d'un autre composé dihydroxy aliphatique Download PDF

Info

Publication number
WO2021254892A1
WO2021254892A1 PCT/EP2021/065741 EP2021065741W WO2021254892A1 WO 2021254892 A1 WO2021254892 A1 WO 2021254892A1 EP 2021065741 W EP2021065741 W EP 2021065741W WO 2021254892 A1 WO2021254892 A1 WO 2021254892A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbonate
process step
catalyst
acid
Prior art date
Application number
PCT/EP2021/065741
Other languages
German (de)
English (en)
Inventor
Alexander Meyer
Thomas Pfingst
Lukas Fabian SCHULZ
Original Assignee
Covestro Deutschland Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland Ag filed Critical Covestro Deutschland Ag
Priority to CN202180043751.XA priority Critical patent/CN115667357A/zh
Priority to JP2022574104A priority patent/JP2023529826A/ja
Priority to US17/918,662 priority patent/US20230340190A1/en
Priority to MX2022016129A priority patent/MX2022016129A/es
Priority to EP21732030.8A priority patent/EP4168469A1/fr
Priority to KR1020227043944A priority patent/KR20230027030A/ko
Publication of WO2021254892A1 publication Critical patent/WO2021254892A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols

Definitions

  • the present invention relates to copolyester carbonates made from cycloaliphatic diacids and 1,4: 3,6-dianhydrohexitols, which contain at least one additional aliphatic diol, and a process for producing the corresponding polyester carbonates.
  • polyesters, polycarbonates and polyester carbonates have good properties in terms of mechanics, heat resistance and weathering resistance.
  • each polymer group has certain key characteristics that distinguish such materials.
  • Polycarbonates, for example, have good mechanical properties, whereas polyesters often show better chemical resistance.
  • polyester carbonates exhibit profiles of properties from both of the groups mentioned.
  • Aromatic polycarbonates or polyesters often have a good profile of properties, but show weaknesses in terms of resistance to aging and weathering. For example, the absorption of UV light leads to yellowing and possibly embrittlement of these thermoplastic materials.
  • aliphatic polycarbonates and polyester carbonates have better properties, in particular better aging and / or weathering resistance and better optical properties (for example transmission).
  • cycloaliphatic alcohols are, for example, TCD alcohol (tricyclodecanedimethanol; 8- (hydroxymethyl) -3-tricyclo [5.2.1.02,6] decanyl] methanol),
  • 3,6-dianhydrohexitols such as isosorbide and the isomers isomannide and iosidide.
  • cycloaliphatic acids such as 1,2, 1,3 or 1,4 cyclohexanedicarboxylic acids or corresponding naphthalene derivatives can also be used as (co) monomers.
  • polyesters or polyester carbonates are then obtained.
  • This application relates to copolyester carbonates based on 1,4: 3,6-dianhydrohexitols such as isosorbide or the isomers as well as cycloaliphatic diacids which contain at least one further dihydroxy compound in order to achieve improved properties.
  • the invention also relates to a process for the production of these copolyester carbonates, which is by the direct Implementation of the raw materials excels and does not require any raw materials that are challenging to handle, such as phosgene.
  • polyesters of cyclohexanedicarboxylic acid and isosorbide are described by Oh et al. in Macromolecules 2013, 46, 2930-2940. However, the present invention is preferably directed to polyester carbonates.
  • Polyesters are produced on an industrial scale, for example, by transesterification of corresponding ester-containing monomers with diols.
  • the polyester is produced from 1,4-cyclohexanedimethanol and 1,4-cyclohexanedicarboxylic acid starting from the dimethyl ester of the diacid (blend of this polyester and polycarbonate: Xyrex ® from DuPont).
  • Example 1 of EP 3026074 A1 describes the direct reaction of the diacid with phenol to give the corresponding ester.
  • example 2 of EP 3026074 A1 a dimethyl ester is reacted with phenol.
  • the yield for both variants of the phenyl ester production can, however, still be improved.
  • the polyester carbonate is then produced.
  • This document thus describes a two-stage process with corresponding disadvantages of several stages such as e.g. B. the complexity, the increased price, the need for several cleaning steps etc.
  • EP 3248999 A1 describes the production of a diphenyl ester in a solvent and using phosgene. Since the subsequent reaction to form the aliphatic polyester carbonate does not require phosgene, the combination of a phosgene process with a transesterification process in one part of the plant is very disadvantageous. The method described in EP 3248999 A1 is therefore not optimal either. A two-step process is also described here.
  • US 2009/105393 A1 discloses an isosorbide-based polycarbonate comprising: an isosorbide unit, an aliphatic unit derived from a C14 to C44 aliphatic diacid, a C14 to 44 aliphatic diol, or a combination thereof; and optionally an additional unit that differs from the isosorbide and the aliphatic units, wherein the isosorbide unit, the aliphatic unit and the additional unit are each carbonates or a combination of carbonate and ester units.
  • the frequent disadvantages of aliphatic polycarbonates or polyester carbonates have already been discussed above.
  • no polymers are produced which are derived from a combination of isosorbide, a cycloaliphatic diacid and, in addition, an aliphatic diol.
  • an activated carbonate is used for transesterification.
  • aromatic polyester carbonates are described, for example, in WO 01/32742 A1.
  • a direct synthesis or also one-pot synthesis is shown, that is, a synthesis in which all the structural elements that will later make up the polyester carbonate are already present as monomers at the beginning of the synthesis.
  • aromatic dihydroxy compounds such as bisphenol A, carboxylic acid diesters and aromatic or linear aliphatic diacids are used as monomers.
  • temperatures of 300 ° C. can be used in the condensation reaction with removal of the phenol formed. The use of such temperatures is not possible in the production of aliphatic polyester carbonates, since aliphatic diols eliminate at this temperature load and / or tend to thermal decomposition.
  • the polyester carbonates which are described in EP 3026074 A1 and in EP 3248999 A1, have high glass transition temperatures.
  • the structure of these polyester carbonates is very rigid. This is in particular a consequence of the isosorbide structure condensed into the polymer chain.
  • the bicyclic substructure increases the glass transition temperature due to its rigid character - however, it makes the polymer chain very inflexible; this can in principle lead to disadvantages.
  • Park et al describe that higher amounts of isosorbide in the polymer decrease the molecular weight (S. A. Park et al. Polymer 2017, 116, 153 - 159; pp. 155/156). The authors describe that the increase in molecular weight is prevented by the high melt viscosity.
  • the cyclohexanedicarboxylic acid increases the flexibility somewhat, but the overall structure of the polymer chain is still quite rigid. This can lead to disadvantages during the production of the polymers. Due to the inflexible character, the reaction partners (chain ends) are more difficult to find with increasing molecular weight. As described above, this results in a limitation of the molecular weight. Furthermore, due to the rigid character, the viscosity rises sharply during the polymer synthesis. To compensate for this, the temperature is often increased during polymer production in the final phase of the polycondensation in order to achieve better flowability. However, this is only possible to a limited extent with aliphatic polymers, since the thermal stability is significantly lower compared to, for example, aromatic polyesters or polycarbonates.
  • the high shear stress can lead to damage, which can result in a deterioration in the optical and mechanical properties.
  • the present invention was therefore based on the object of providing a process for the production of polyester carbonates, comprising at least one 1,4: 3,6-dianhydrohexitol and at least one cycloaliphatic dicarboxylic acid, which is characterized by good surface renewal of manufacturing. Better surface renewal can be recognized, for example, by higher achievable molecular weights. In particular, this should enable sufficiently high molecular weights to be achieved for the polyester carbonates.
  • “sufficiently high molecular weights” is preferably understood to mean a polymer which has a relative solution viscosity above 1.22, preferably 1.25 to 1.65, more preferably 1.28 to 1.63 and particularly preferably from 1.30 to 1.62 each measured in dichloromethane at a concentration of 5 g / 1 at 25 ° C. with an Ubbeloh viscometer.
  • the polyester carbonates according to the invention should therefore have better processing properties and good mechanical properties.
  • the object was to provide the simplest possible method for producing polyester carbonates by means of melt transesterification.
  • “simple” is to be understood in particular as a process which is inexpensive in terms of apparatus, comprises a few stages, in particular purification stages, and / or is therefore economically and also ecologically advantageous.
  • the process according to the invention should manage without starting materials which are challenging to handle, in particular phosgene.
  • At least one, preferably all of the above-mentioned objects have been achieved by the present invention. It has surprisingly been found that the synthesis of a polyester carbonate from at least one cycloaliphatic diacid, at least one diaryl carbonate, at least one 1.4: 3,6-dianhydrohexitol and at least one further aliphatic dihydroxy compound by means of melt transesterification in a direct synthesis or one-pot synthesis, in which all of the structural elements which later make up the polyester carbonate are already present as monomers at the beginning of the synthesis.
  • the process for producing a polyester carbonate according to the invention can be described schematically, for example, by the reaction of cyclohexanedicarboxylic acid, isosorbide, an additional diol HO-R-OH and diphenyl carbonate, as follows:
  • the method according to the invention thus gives a polymer which has a different statistical distribution of the different blocks than a polymer which is obtained from a cyclohexanediphenyl ester, isosorbide, another diol and diphenyl carbonate.
  • a method for producing a polyester carbonate by means of melt transesterification comprising the steps
  • process step (i) at least one reaction of at least one cycloaliphatic dicarboxylic acid with at least one diaryl carbonate takes place.
  • further reactions are caused by the presence of the at least one 1,4: 3,6-dianhydrohexitol (hereinafter also component (A) and the at least one further aliphatic dihydroxy compound (hereinafter also component (B )).
  • the Process step (i) form oligomers which have a mass separation in the MALDI-ToF mass spectrometer which corresponds to a unit of component (A) and / or component (B) with carbonate (with loss of the two hydroxyl groups).
  • process step (i) is preferably carried out until a substantial decrease in gas formation can be observed, and only then process step (ii) is initiated, for example by applying a vacuum to remove the chemical compound split off during the condensation.
  • process steps (i) and (ii) cannot, however, according to the invention, be sharply separated from one another.
  • the process according to the invention is referred to as direct synthesis or also one-pot synthesis, since in process step (i) all structural elements which later make up the polyester carbonate are already present as monomers.
  • This preferably means that, according to the invention, all aliphatic dihydroxy compounds (in each case components (A) and (B)), all cycloaliphatic dicarboxylic acids and also all diaryl carbonates are present in this step, even if more than just the dihydroxy Compounds of components (A) and (B), a cycloaliphatic dicarboxylic acid and / or a diaryl carbonate. It is therefore preferred according to the invention that all monomers which are condensed to the polyester carbonate in process step (ii) are already present during process step (i).
  • the embodiment in which a small proportion of the at least one diaryl carbonate is additionally added in process step (ii) can also be included according to the invention. This can be used specifically to reduce the OH end group content of the resulting polyester carbonate. Such a procedure is described in JP2010077398 A, for example. In this case, however, it is necessary that the at least one diaryl carbonate added in small amounts in process step (ii) corresponds to the at least one diaryl carbonate present in process step (i), so that all structural elements which later make up the polyester carbonate are still present as monomers in process step (i) and no further structural elements are added. In this sense, one can still speak of a direct synthesis or one-pot synthesis.
  • aromatic dihydroxy compounds and / or aromatic dicarboxylic acids are present in process step (i).
  • these are preferably only present in small proportions.
  • Particularly preferred in process step (i) are additionally up to 20 mol%, further preferably up to 10 mol% and very particularly preferably up to 5 mol% of an aromatic dihydroxy compound (component (C)), based on the total Amount of substance of the dihydroxy compound used is present.
  • process step (i) in addition, if appropriate in addition to the aromatic dihydroxy compound, up to 20 mol%, further preferably up to 10 mol% and very particularly preferably up to 5 mol% of an aromatic dicarboxylic acid is present in relation to the total amount of substance of the dicarboxylic acid used.
  • an aliphatic polyester carbonate is preferably still used according to the invention.
  • no aromatic dicarboxylic acid is used in process step (i). It is likewise preferred that neither an aromatic dihydroxy compound nor an aromatic dicarboxylic acid is used in process step (i).
  • aromatic compounds in polyester carbonates reduce their UV stability and weather resistance. This is particularly disadvantageous for outdoor applications.
  • aromatic components in a polyester carbon reduce the surface hardness of molded articles made from it, which may lead to the need for painting.
  • diphenyl esters of aromatic acids, for example, which can be formed as intermediates are stable intermediates which can slow down the polycondensation. This means that further specific catalysts may have to be used.
  • additional aromatic dihydroxy compounds are preferably selected from the group consisting of bisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), bisphenol B, bisphenol M, the bisphenols (I) to (III) where in these formulas (I) to (III) R 'each represents C1-C4-alkyl, aralkyl or aryl, preferably methyl or phenyl, very particularly preferably methyl.
  • aromatic dicarboxylic acids are preferably selected from the group consisting of isophthalic acid, terephthalic acid, 2,5-furandicarboxylic acid and 2,6-naphthalene dicarboxylic acid. It is known that small proportions of these aromatic diacids can reduce the water absorption of an aliphatic polyester carbonate.
  • At least one 1.4: 3,6-dianhydrohexitol is used as component (A) in process step (i).
  • 1,4: 3,6-dianhydrohexitols are generally selected from the group consisting of isomannide, isoidide and isosorbide. This can be a bio-based structural element, with all the advantages of a bio-based monomer and the resulting polymer (e.g. better sustainability, since it is accessible from renewable raw materials).
  • the method according to the invention is particularly preferably characterized in that the at least one 1,4: 3,6-dianhydrohexitol is isosorbide. It is preferred that component (A) consists of isosorbide.
  • At least one further aliphatic dihydroxy compound (component (B)) is used in process step (i). It is preferred that component (B) consists of two further aliphatic dihydroxy compounds. It is also preferred that component (B) consists of a further aliphatic dihydroxy compound. It is therefore particularly preferred that component (A) consists of isosorbide and component (B) consists of a further aliphatic dihydroxy compound. If appropriate, a component (C) which comprises an aromatic dihydroxy compound can also be present in the mixture of dihydroxy compounds (see above).
  • the at least one further aliphatic dihydroxy compound has the chemical formula (I):
  • X represents a linear alkylene group with 2 to 22, preferably 2 to 15 carbon atoms, particularly preferably 2 to 10 carbon atoms, which can optionally be interrupted by at least one heteroatom
  • X represents a linear alkylene group with 2 to 22, preferably 2 to 15 carbon atoms, particularly preferably 2 to 10 carbon atoms, which can optionally be interrupted by at least one heteroatom
  • X is a linear alkylene group which can optionally be interrupted by at least one heteroatom, it preferably has 2 to 15, particularly preferably 2 to 12, very particularly preferably 2 to 11, particularly preferably 2 to 10, more preferably 2 to 6 and more preferably 3 to 4 carbon atoms.
  • the hetero atom which can optionally interrupt the alkylene group is preferably oxygen or sulfur, particularly preferably oxygen.
  • the alkylene group particularly preferably contains only one heteroatom or no heteroatom. If at least one heteroatom is present in the alkylene group, the stated number of carbon atoms relates to the total number of carbon atoms in the alkylene group. For example, the group -CH2-CH2-O-CH2-CH2- contains 4 carbon atoms.
  • the linear alkylene group, which is optionally interrupted by at least one heteroatom has fewer than 12, particularly preferably fewer than 10, carbon atoms.
  • the alkylene group particularly preferably has no heteroatom.
  • X is a branched alkylene group having 4 to 20, preferably 5 to 15 carbon atoms, particularly preferably 5 to 11 carbon atoms, very particularly preferably 5 to 10 carbon atoms, which can optionally be interrupted by at least one heteroatom
  • the heteroatom which can optionally interrupt the branched alkylene group is preferably oxygen or sulfur, particularly preferably oxygen.
  • the branched alkylene group particularly preferably contains only one heteroatom or no heteroatom.
  • the branched alkylene group particularly preferably has no heteroatom.
  • the term “branched” is understood to mean the branches on aliphatic carbon chains known to the person skilled in the art.
  • the branched alkylene group preferably comprises at least one tertiary and / or at least one quaternary carbon atom.
  • the branches preferably have chain lengths of 1 to 5 carbon atoms, particularly preferably 1 to 4, very particularly preferably 1 to 3 carbon atoms. These carbon atoms of the branches count towards the total number of carbon of the branched alkylene group.
  • a branched alkylene group of -CH2-C (CH3) 2-CH2- has 5 carbon atoms.
  • X is a cycloalkylene group having 4 to 20, preferably 5 to 15 carbon atoms, which can optionally be interrupted by at least one heteroatom and where the cycloalkylene group can optionally contain several rings and each may optionally be branched, so the above statements apply to the heteroatom.
  • the heteroatom which can optionally interrupt the cycloalkylene group is preferably oxygen or sulfur, particularly preferably oxygen.
  • the cycloalkylene group particularly preferably contains only one heteroatom or no heteroatom.
  • the cycloalkylene group particularly preferably has no heteroatom.
  • the cycloalkylene group preferably has at least one, preferably one, cylcus with 4 to 6 carbon atoms.
  • the cycloalkylene group has a total of 4 to 20, preferably 5 to 15 carbon atoms and a cycle with 4 to 5 carbon atoms.
  • the carbon atoms of the cycle are added to the total number of carbon atoms in the cycloalkylene group.
  • a tetramethylcyclobutenyl group has a total of 8 carbon atoms with a cycle with 4 carbon atoms.
  • the cycloalkylene group can have at least one branch. This is particularly preferred. If branches are present, then these can be present in the cycloaliphatic chain and / or the cycle which may be present. The branches are preferably present in the cycle.
  • X is preferably a cycloalkylene group with 5 to 15 carbon atoms with a cycle which optionally has at least one branch, preferably has at least one branch and at least one cycle, preferably a cycle with 4 to 6 carbon atoms, particularly preferably 4 to Has 5 carbon atoms.
  • the at least one further aliphatic dihydroxy compound has 2 to 10 carbon atoms.
  • the method according to the invention is particularly preferably characterized in that the at least one further aliphatic dihydroxy compound is selected from the group consisting of 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-Cyclohexanedimethanol, 1,4-Cyclohexanedimethanol, 2,2-bis (4-Hydroxycyclohexyl) propane, tetrahydro-2,5-furandimethanol, 2-butyl-2-ethyl-1,3-propanediol, 2- (2 - Hydroxyethoxy) ethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1 , 1-d
  • the at least one further aliphatic dihydroxy compound is selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2- (2-hydroxyethoxy) ethanol, 2, 2,4, 4- tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, cyclobutan-1,1-diyldimethanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and any mixtures thereof.
  • the at least one further aliphatic dihydroxy compound is selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2- Dimethylpropane-1,3-diol, cyclobutane-1,3-diyldimethanol, 1,4-butanediol and any mixtures thereof.
  • the at least one further aliphatic dihydroxy compound is selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2,2,4,4-tetramethyl-1,3, 3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1,3-diyldimethanol and any mixtures thereof.
  • the additional at least one further aliphatic dihydroxy compound can react with the at least one diaryl carbonate which is also present under the reaction conditions of process step (i) according to the invention. This is observed in particular in the case of those dihydroxy compounds in which the two hydroxyl groups are in spatial proximity to one another (for example 2 or 3 carbon atoms away from one another). Without wishing to be bound by a theory, an intramolecular carbonate appears to be formed which is no longer reactive. This means that this intramolecular carbonate no longer takes part in the reaction to form the polyester carbonate.
  • the amount of the at least one further aliphatic dihydroxy compound which is added at the beginning of process step (i) does not always necessarily correspond to the amount of structural elements in the polyester carbonate derived from this dihydroxy compound. As a rule, it will be lower, especially in the case of compounds which have two hydroxy compounds in close proximity to one another. In particular, this does not apply to cyclic dihydroxy compounds such as cyclohexanedimethanol.
  • the person skilled in the art is familiar with methods of how to determine the proportions of structural units in the resulting polyester carbonate. These can preferably be determined via 'H-NMR. This method is known to the person skilled in the art.
  • the polyester carbonate can, for example, be dissolved in CDCF and the corresponding peaks of the structural units can be identified. The proportions and proportions can be determined via the integrals.
  • At least one cycloaliphatic dicarboxylic acid is also used in process step (i). It is preferred that the at least one cycloaliphatic dicarboxylic acid is selected from a compound of the chemical formula (Ha), (IIb) or mixtures thereof worm
  • B each independently of one another represents a Cfb group or a heteroatom which is selected from the group consisting of O and S, preferably a CH2 group or an oxygen atom,
  • Ri each independently represents a single bond or an alkylene group with 1 to 10 carbon atoms, preferably a single bond or an alkylene group with 1 to 5 carbon atoms, particularly preferably a single bond, and n is a number between 0 and 3, preferably 0 or 1.
  • Ri represents a single bond
  • Ri thus comprises zero carbon atoms.
  • the at least one cycloaliphatic dicarboxylic acid is selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, tetradihydro-2,5-furandicarboxylic acid, tetradihydro-2,5 -dimethyl furandicarboxylic acid decahydro-2,4-naphthalenedicarboxylic acid, decahydro-2,5-naphthalenedicarboxylic acid, decahydro-2,6-naphthalenedicarboxylic acid and decahydro-2,7-naphthalenedicarboxylic acid. Any mixtures can also be used. It is very particularly preferably 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or 1,2-cyclohexanedicarboxy
  • cycloaliphatic acid small amounts of other aliphatic acids can also be used.
  • up to 20 mol%, more preferably up to 10 mol% and very particularly preferably up to 5 mol% of a further aliphatic acid which is not a cycloaliphatic acid are particularly preferably also present.
  • the further aliphatic acid is preferably selected from the group consisting of 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, 2,2,5-trimethyladipic acid and 3,3-dimethylglutaric acid.
  • at least one diaryl carbonate is also used in process step (i). It is preferred that the at least one diaryl carbonate is selected from the group consisting of a compound of the formula (2) wherein
  • R, R 'and R can each independently be the same or different and represent hydrogen, optionally branched Cl-C34-alkyl, C7-C34-alkylaryl, C6-C34-aryl, a nitro group, a carbonyl-containing group, a carboxyl-containing group Group or a halogen group.
  • R, R 'and R are each independently identical or different and represent hydrogen, optionally branched C1-C34-alkyl, C7-C34-alkylaryl, C6-C34-aryl, a nitro group, a carbonyl containing group or a halogen group.
  • the at least one diaryl carbonate is preferably diphenyl carbonate, 4-tert-butylphenyl-phenyl-carbonate, di- (4-tert-butyl-phenyl) -carbonate, biphenyl-4-yl-phenyl-carbonate, di- (biphenyl-4) -yl) carbonate, 4- (l -methyl-1-phenylethylj-phenyl-phenyl-carbonate, di- [4- (l-methyl-1-phenylethyl) -phenyl] -carbonate, bis (methylsalicyl) carbonate, bis (ethylsalicyl) carbonate, bis (propylsalicyl) carbonate, bis (2-benzoylphenyl carbonate),
  • the at least one diaryl carbonate is preferably diphenyl carbonate, 4-tert-butylphenylphenyl carbonate, di- (4-tert-butylphenyl) carbonate, biphenyl-4-ylphenyl carbonate, di- (biphenyl-4) -yl) carbonate, 4- (1-methyl-1-phenylethyl-phenyl-carbonate, di- [4- (1-methyl-1-phenylethyl-phenyl] carbonate), bis (2-benzoylphenyl carbonate), bis (phenylslicyl) carbonate and / or
  • the at least one diaryl carbonate is particularly preferably diphenyl carbonate, 4-tert-butylphenylphenyl carbonate, di- (4-tert-butylphenyl) carbonate, biphenyl-4-ylphenyl carbonate , Di- (biphenyl-4-yl) carbonate, 4- (1-methyl-1-phenylethylj-phenyl-phenyl-carbonate and / or di- [4- (1-methyl-1-phenylethylj-phenyl] -carbonate).
  • the at least one diaryl carbonate diphenyl carbonate is particularly preferred.
  • At least one catalyst is present in process step (i).
  • This is preferably an inorganic base and / or an organic catalyst.
  • the at least one catalyst is particularly preferably an inorganic or organic base with a pK ⁇ value of at most 5.
  • the at least one inorganic base or the at least one organic catalyst is selected from the group consisting of lithium, sodium, potassium, cesium, calcium, barium, magnesium, hydroxides, - carbonates, -halides, -phenolates, -diphenolates, -fluorides, -acetates, -phosphates, -hydrogenphosphates, -boranates, tetramethylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium fluoride, tetramethyl-boroniumoxid, tetramethyl-boroniumoxidium, phenyl-boronium-tetraphenyl-fluorophosphonium-fluorophosphonium-phenyl-phosphonaphenyl-phenyl-phosphonaphenyl-phenyl-phosphonaphenyl-phosphonaphenyl-phosphonaphenyl-phosphonaphenyl-phosphonaphenyl-phosphonaphenyl-
  • the at least one catalyst is particularly preferably an organic base, preferably those mentioned above, very particularly preferably alkylamines, imidazole (derivatives), guanidine bases such as triazabicyclodecene, DMAP and corresponding derivatives, DBN and DBU, most preferably DMAP.
  • organic base preferably those mentioned above, very particularly preferably alkylamines, imidazole (derivatives), guanidine bases such as triazabicyclodecene, DMAP and corresponding derivatives, DBN and DBU, most preferably DMAP.
  • the at least one catalyst is preferably used in amounts of 1 to 5000 ppm, preferably 5 to 1000 ppm and particularly preferably 20 to 200 ppm, based on 1 mol of the cycloaliphatic dicarboxylic acid.
  • the process according to the invention is characterized in that the reaction in process step (i) is carried out in the presence of at least one first catalyst and / or a second catalyst and the condensation in process step (ii) is carried out at least in the presence of the first catalyst and the second Catalyst carried out where the first catalyst is at least one tertiary nitrogen base, the second catalyst is at least one basic compound, preferably a basic alkali metal salt, and the proportion of alkali metal cations in process step (ii) being 0.0008 to 0.0050% by weight on all components used in process step (i).
  • a first catalyst and / or a second catalyst is therefore present in process step (i).
  • the first catalyst is a tertiary nitrogen base.
  • This first catalyst is preferably selected from bases derived from guanidine, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene , 1,5,7-
  • DMAP 4-dimethylaminopyridine
  • 1,8-diazabicyclo [5.4.0] undec-7-ene 1,8-diazabicyclo [5.4.0] undec-7-ene
  • 1,5-diazabicyclo [4.3.0] non-5-ene 1,5,7-
  • the first catalyst is more preferably selected from bases derived from guanidine, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene , l, 5,7-triazabicyclo [4.4.0] dec-5-en.
  • DMAP 4-dimethylaminopyridine
  • 1,8-diazabicyclo [5.4.0] undec-7-ene 1,5-diazabicyclo [4.3.0] non-5-ene
  • l 5,7-triazabicyclo [4.4.0] dec-5-en.
  • 4-Dimethylaminopyridine is particularly preferably used.
  • the first catalyst is preferably used in an amount of 0.002 to 0.10% by weight, more preferably in an amount of 0.005 to 0.050% by weight, particularly preferably in an amount of 0.008 to 0.030% by weight, based in each case on all in process step (i) components used.
  • the second catalyst is selected from the group consisting of inorganic or organic alkali salts and inorganic or organic alkaline earth salts.
  • the alkali metal cations contained in process step (ii) are lithium cations, potassium cations, sodium cations, cesium cations and mixtures thereof.
  • the second catalyst used is the organic or inorganic alkali or alkaline earth metal salt, preferably of a weak acid (pK a between 3 and 7 at 25 ° C.).
  • Suitable weak acids are, for example, carboxylic acids, preferably C2-C22 carboxylic acids, such as acetic acid, propionic acid, oleic acid, stearic acid, lauric acid, benzoic acid, 4-methoxybenzoic acid, 3-methylbenzoic acid, 4-tert.-butylbenzoic acid, p-toluene acetic acid, 4-hydroxybenzoic acid, salicylic acid Partial esters of polycarboxylic acids, such as, for example, monoesters of succinic acid, branched aliphatic carboxylic acids, such as 2,2-dimethylpropanoic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2-ethylhexanoic acid.
  • organic or inorganic alkali metal or alkaline earth metal salt of a strong acid such as, for example, hydrochloric acid.
  • Suitable organic and inorganic salts are or are derived from sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, lithium carbonate, potassium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium tearate, potassium stearate, lithium stearate, sodium oleate, lithium oleate, potassium oleate, sodium benzoate, potassium benzoate Dipotassium and dilithium salts of BPA.
  • Calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate and corresponding oleates can also be used. It is also possible to use corresponding salts of phenols, in particular of phenol. These salts can be used individually or as a mixture.
  • the second catalyst is preferably selected from the group consisting of sodium hydroxide, lithium hydroxide, sodium phenolate, lithium phenolate, sodium benzoate, lithium benzoate, lithium chloride, lithium acetylacetonate and cesium carbonate and mixtures of these substances.
  • Sodium phenolate, lithium phenolate, sodium hydroxide, lithium hydroxide, sodium benzoate, lithium benzoate, lithium chloride and / or lithium acetyl cetonate are particularly preferably used.
  • Lithium chloride is preferably used as an aqueous solution, for example in the form of a 15% solution.
  • the molar ratio of all aliphatic dihydroxy compounds present in process step (i) to all cycloaliphatic dicarboxylic acids present in process step (i) before the reaction in process step (i) is preferably 1: 0.6 to 1: 0.05, more preferably 1: 0.5 to 1: 0.15 and very particularly preferably 1: 0.4 to 1: 0.2.
  • the ratio of aliphatic dihydroxy compounds and cycloaliphatic dicarboxylic acids in the subsequent polyester carbonate should preferably not be too high (ie not too few cycloaliphatic dicarboxylic acids incorporated) in order to achieve particularly favorable mechanical properties, good chemical resistance and good processing properties.
  • Polymers with a high content of units derived from dihydroxy compounds such as isosorbide are mostly very rigid and therefore have inadequate mechanical properties. If the content of cycloaliphatic dicarboxylic acids derived units is too low, the processing properties of the polymers also deteriorate.
  • the polyester units generally lead to better chemical resistance of the polyester carbonate, which is why the content of units derived from cycloaliphatic dicarboxylic acids should also not be too low.
  • the polyester carbonate produced have a relative solution viscosity eta rel of greater than 1.22, also preferably from 1.25 to 1.65, particularly preferably 1.28 to 1.63, very particularly preferably 1.30 to 1, 62 has. It is preferred here that the relative solution viscosity in dichloromethane at a concentration of 5 g / 1 at 25 ° C. is measured with an Ubbeloh viscometer. The Lachmann knows how to determine the relative solution viscosity using an Ubbeloh viscometer. According to the invention, this is preferred in accordance with DIN 51562-3; Conducted 1985-05.
  • the throughput times of the polyester carbonate to be measured are measured by the Ubbelohde viscometer in order to then determine the viscosity difference between the polymer solution and its solvent.
  • the Ubbelohde viscometer is first calibrated by measuring the pure solvents dichloromethane, trichlorethylene and tetrachlorethylene (at least 3 measurements, a maximum of 9 measurements). The actual calibration then takes place with the solvent dichloromethane. The polymer sample is then weighed, dissolved in dichloromethane and the flow time for this solution is then determined three times. The mean value of the flow times is corrected using the Hagenbach correction and the relative solution viscosity is calculated.
  • these molar masses are preferably referred to as “sufficient” molar mass.
  • isosorbide preferably 65-85 parts isosorbide, or isosorbide isomer 40 to 10 parts cycloaliphatic dicarboxylic acid, preferably 35-15 parts cycloaliphatic dicarboxylic acid, preferably 1.4 cyclohexanedicarboxylic acid 2 to 25 mol%, preferably 3 to 20 mol% in particular preferably 4 to 18 mol% of isosorbide is replaced by the at least one further aliphatic diol, in particular linear, very preferably branched diol with 2 to 10 carbon atoms.
  • the total amount of at least one aliphatic diol in the overall composition is preferably less than 20 mol%, in particular less than 15 mol%.
  • the method according to the invention is characterized in that carbon dioxide is released during the process.
  • carbon dioxide is preferably split off in process step (i) (see reaction scheme above). This procedure allows a quick reaction under low temperature stress.
  • process step (i) preferably comprises at least one, particularly preferably all of the following steps (ia) to (ic):
  • Step (ia) Melting all of the components present in process step (i), ie at least the at least one cycloaliphatic dicarboxylic acid, the at least one diaryl carbonate and at least the components (A) and (B) in the presence of the at least one catalyst. This is preferably done under a protective gas atmosphere, preferably under nitrogen and / or argon. Step (ia) is preferably carried out in the absence of a solvent.
  • solvent is known to Lachmann in this context. According to the invention, the term “solvent” is preferably understood to mean a compound which does not enter into a chemical reaction in any of process steps (i) and (ii).
  • step (ib) heating the mixture, preferably the melt obtained from step (ia).
  • Step (ia) and step (ib) can also overlap, since heating may also be necessary to generate a melt in step (ia).
  • the heating is preferably carried out initially to 150.degree. C. to 180.degree.
  • step (ic) Reaction of the mixture, preferably the mixture obtained from step (ib), with the introduction of mixing energy, preferably by stirring.
  • step (ic) can overlap with step (ib), since the reaction of the mixture can already be initiated by heating.
  • the melt is preferably already heated to temperatures between 150 and 180 ° C. by step (ib) under normal pressure. Depending on the selected catalyst, the temperature can be left in the range 160 - 200 ° C.
  • the temperature in step (ic) is gradually increased - depending on the observed reactivity - to 200.degree. C.-300.degree. C., preferably 210-260.degree. C., particularly preferably 215-240.degree.
  • the reactivity can be estimated via the gas evolution in a manner known to the person skilled in the art. In principle, higher temperatures are also used in this step possible, but secondary reactions can occur at higher temperatures (e.g. discoloration). Therefore, higher temperatures are less preferred.
  • the mixture is stirred under normal pressure until the evolution of gas essentially stops. According to the invention it is possible that under these conditions the aryl alcohol formed by the reaction of the at least one carboxylic acid with the at least one diaryl carbonate (for example phenol when using diphenyl carbonate) is already partially removed.
  • oligomers comprising carbonate units from the reaction of the at least one of the dihydroxy compounds (A) and / or (B) with the at least one diaryl carbonate and / or ester units from the reaction of the at least one of the dihydroxy compounds (A) and / or ( B) can be detected with the at least one dicarboxylic acid.
  • the reaction time in step (ic) depends on the amount of starting materials.
  • the reaction time of step (ic) is preferably between 0.5 h and 24 h, preferably between 0.75 h and 5 h and particularly preferably between 1 h and 3 h. It is preferred to choose the reaction time so that the evolution of gas has essentially subsided (see reaction scheme above).
  • the molar ratio of the sum of all dihydroxy compounds present in process step (i) and all cycloaliphatic dicarboxylic acids present in process step (i) to all diaryl carbonates present in process step (i) before the reaction in process step (i) 1: 0.4 to 1: 1.6, preferably 1: 0.5 to 1: 1.5, furthermore preferably 1: 0.6 to 1: 1.4, particularly preferably 1: 0.7 to 1: 1, 3, particularly preferably 1: 0.8, to 1: 1.2 and very particularly preferably 1: 0.9 to 1: 1.1.
  • the person skilled in the art is able to select appropriate optimally suitable ratios depending on the purity of the starting substances.
  • process step (ii) the further condensation of the mixture obtained from process step (i) takes place at least with removal of the chemical substances split off during the condensation Connection.
  • the expression “further” condensation is to be understood as meaning that condensation has already taken place at least partially in process step (i). This is preferably the reaction of the at least one cycloaliphatic dicarboxylic acid with the at least one diaryl carbonate with elimination of an aryl alcohol.
  • a further condensation to give oligomers has preferably already taken place (see process step (i)).
  • the proportion of alkali metal cations in process step (ii) is preferably from 0.0009 to 0.0005% by weight and particularly preferably from 0.0010 to 0.0045% by weight, based in each case on all components used in process step (i).
  • the first catalyst and the second catalyst are present in process step (i).
  • the total amount of the first and / or the second catalyst is preferably used in process step (i). Most preferably, the total amount of both catalysts is used in process step (i).
  • condensation is known to the person skilled in the art. This is preferably understood to mean a reaction in which two molecules (of the same substance or different substances) combine to form a larger molecule, one molecule of a chemically simple substance being split off. This compound split off during the condensation is removed in process step (ii). It is preferred here that the chemical compound split off during the condensation is removed in process step (ii) by means of a vacuum. Accordingly, it is preferred that the process according to the invention is characterized in that during the reaction in process step (i) the volatile constituents, which have a boiling point below the cycloaliphatic diester formed in process step (i), the mixture of dihydroxy compound and below the at least one Have diaryl carbonate, optionally separated with gradual reduction of the pressure.
  • a step-by-step separation is preferred if different volatile constituents are separated off. as well A step-by-step separation is preferably chosen in order to ensure that the volatile constituent or constituents are separated off as completely as possible.
  • the volatile constituents are the chemical compounds or compounds split off during condensation.
  • a step-by-step lowering of the pressure can take place, for example, in such a way that as soon as the head temperature drops, the pressure is lowered in order to ensure a continuous removal of the chemical compound split off during the condensation.
  • a pressure of 1 mbar, preferably ⁇ Imbar is reached, condensation continues until the desired viscosity is reached. This can be done, for example, by checking the torque, i.e. the polycondensation is terminated when the desired torque of the stirrer is reached.
  • the condensation product is separated off in process step (ii) preferably at temperatures of 200.degree. C. to 280.degree. C., particularly preferably 210.degree. C. to 260.degree. C. and particularly preferably 220.degree. C. to 250.degree.
  • the vacuum during the separation is preferably from 500 mbar to 0.01 mbar. In particular, it is preferred that the separation takes place gradually by reducing the vacuum.
  • the vacuum in the last stage is very particularly preferably 10 mbar to 0.01 mbar.
  • a polyester carbonate is provided which is obtained by the above-described process according to the invention in all of the disclosed combinations and preferences.
  • the polyester carbonate according to the invention can be processed as such into moldings of all kinds. It can also be processed with other thermoplastics and / or polymer additives to form thermoplastic molding compounds.
  • the molding compositions and moldings are further objects of the present invention.
  • the polymer additives are preferably selected from the group consisting of flame retardants, antidripping agents, flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g. hydrolysis, heat aging and UV stabilizers and transesterification inhibitors),
  • thermoplastic molding compositions can be produced, for example, by mixing the polyester carbonate and the other constituents in a known manner and melt-compounding and melt-extruding them at temperatures of preferably 200 ° C. to 320 ° C. in conventional units such as internal kneaders, extruders and twin-screw screws. This process is generally referred to as compounding in the context of this application. Molding compound is understood to mean the product that is obtained when the constituents of the composition are melt-compounded and melt-extruded.
  • the moldings made from the polyester carbonate according to the invention or the thermoplastic molding compositions containing the polyester carbonate can be produced, for example, by injection molding, extrusion and blow molding processes. Another form of processing is the production of moldings by deep drawing from previously produced sheets or foils.
  • Cyclohexanedicarboxylic acid 1,4-cyclohexanedicarboxylic acid; CAS 1076-97-7 99%; Tokyo Chemical Industries, Japan, abbreviated as CHDA.
  • the CHDA contained less than 1ppm sodium by elemental analysis
  • Diphenyl carbonate Diphenyl carbonate, 99.5%, CAS 102-09-0; Acros Organics, Geel, Belgium, abbreviated as DPC
  • Isosorbide Isosorbide (CAS: 652-67-5), 99.8%, Polysorb PS A; Roquette Freres (62136 Lestrem, France); abbreviated as ISB
  • Lithium hydroxide monohydrate (CAS: 1310-66-3); > 99.0%; Sigma-Aldrich 2-butyl-2-ethyl-1,3-propanediol: CAS-No .: 115-84-4; Aldrich (abbreviated as BEPD)
  • 1,4-butanediol CAS: 110-63-4; Merck 99%; (abbreviated as BDO)
  • 1,12-dodecanediol CAS: 5675-51-4, Aldrich 99% (abbreviated as DDD)
  • the relative solution viscosity (qrcl; also referred to as eta rel) was determined in dichloromethane at a concentration of 5 g / 1 at 25 ° C. using an Ubbeloh viscometer. The determination was carried out according to DIN 51562-3; 1985-05. The throughput times of the polyester carbonate to be measured are measured by the Ubbelohde viscometer in order to then determine the viscosity difference between the polymer solution and its solvent. This will be First the Ubbelohde viscometer was calibrated by measuring the pure solvents dichloromethane, trichlorethylene and tetrachlorethylene (at least 3 measurements, at most 9 measurements). The actual calibration then takes place with the solvent dichloromethane. The polymer sample is then weighed, dissolved in dichloromethane and the flow time for this solution is then determined three times. The mean value of the flow times is corrected using the Hagenbach correction and the relative solution viscosity is calculated.
  • the glass transition temperature was measured by means of dynamic differential calorimetry (DSC) according to the standard DIN EN ISO 11357-1: 2009-10 and ISO 11357-2: 2013-05 at a heating rate of 10 K / min under nitrogen with determination of the glass transition temperature (Tg) as Turning point determined in the second heating process.
  • DSC dynamic differential calorimetry
  • the sample was dissolved in chloroform. Dithranol with LiCl was used as the matrix. The samples were analyzed in positive reflector and linear modes.
  • the mixture was stirred at 160 ° C. for 40 minutes, at 175 ° C. for 60 minutes, at 190 ° C. for 30 minutes and at 205 ° C. for 10 minutes.
  • carbon dioxide develops continuously.
  • the bath temperature was set to 220 ° C.
  • vacuum was applied.
  • the pressure was reduced to 10 mbar within 30 minutes. Phenol was continuously removed.
  • the mixture was stirred at 10 mbar for about 10 minutes. Then the pressure was reduced to ⁇ Imbar (approx. 0.7 mbar) and condensation was continued for a further 10 minutes. Then the approach was stopped.
  • Examples 1 to 12 according to the invention show that the inventive method provides the desired polyester carbonates in high viscosities as long as the isosorbide to CHDA ratios according to the invention are maintained. It can be seen that the addition of a further aliphatic diol, in particular branched diols, significantly increases the molecular weight compared to an example in which no further aliphatic diol is present (see comparative example 1). A better miscibility could be observed at higher temperatures, so that a further increase in molecular weight could take place. In addition, it is surprising that polymers with certain ISB + further aliphatic diol: CHDA ratios do not show a good increase in molecular weight.
  • Comparative Example 2 shows that ratios with larger proportions of cyclohexanedicarboxylic acid do not lead to the desired polymers or the molecular weights obtained are very low. This was neither known nor deducible from the literature. In the as yet unpublished patent application PCT / EP2019 / 084847 it has already been found that the ISB: CHDA ratio over the broadly defined range according to the invention leads to a good increase in molecular weight, but not outside this range. The addition of at least one further aliphatic diol leads, as can be seen from the comparison with Comparative Example 1, to an additional increase in molecular weight (see above).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un carbonate de polyester à base de diacides cycloaliphatiques et d'au moins un 1,4 : 3,6 - dianhydrohexitol et d'au moins un autre composé dihydroxy aliphatique, le carbonate de polyester préparé selon le procédé et un composé de moulage et un produit moulé contenant le carbonate de polyester. Le procédé selon l'invention est une synthèse directe, dans laquelle tous les éléments structuraux formant le carbonate de polyester suivant sont déjà présents en tant que monomères dans la première étape de procédé.
PCT/EP2021/065741 2020-06-19 2021-06-11 Carbonates de polyester obtenus à partir de diacides cycloaliphatiques, de 1,4 : 3,6-dianhydrohexitol et d'un autre composé dihydroxy aliphatique WO2021254892A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN202180043751.XA CN115667357A (zh) 2020-06-19 2021-06-11 由脂环族二酸、1,4:3,6-二脱水己糖醇和其它脂族二羟基化合物制成的聚酯碳酸酯
JP2022574104A JP2023529826A (ja) 2020-06-19 2021-06-11 脂環式二酸、１，４：３，６－ジアンヒドロヘキシトール、及び更なる脂肪族ジヒドロキシ化合物からのポリエステルカーボネート
US17/918,662 US20230340190A1 (en) 2020-06-19 2021-06-11 Polyester Carbonates From Cycloaliphatic Diacids, 1,4:3,6-Dianhydrohexitol and a Further Aliphatic Dihydroxy Compound
MX2022016129A MX2022016129A (es) 2020-06-19 2021-06-11 Carbonatos de poliester de diacidos cicloalifaticos, 1,4:3,6-dianhidrohexitol y un compuesto dihidroxi alifatico adicional.
EP21732030.8A EP4168469A1 (fr) 2020-06-19 2021-06-11 Carbonates de polyester obtenus à partir de diacides cycloaliphatiques, de 1,4 : 3,6-dianhydrohexitol et d'un autre composé dihydroxy aliphatique
KR1020227043944A KR20230027030A (ko) 2020-06-19 2021-06-11 시클로지방족 이산, 1,4:3,6-디안히드로헥시톨 및 추가의 지방족 디히드록시 화합물로부터의 폴리에스테르 카르보네이트

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20181051 2020-06-19
EP20181051.2 2020-06-19

Publications (1)

Publication Number Publication Date
WO2021254892A1 true WO2021254892A1 (fr) 2021-12-23

Family

ID=71111304

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2021/065741 WO2021254892A1 (fr) 2020-06-19 2021-06-11 Carbonates de polyester obtenus à partir de diacides cycloaliphatiques, de 1,4 : 3,6-dianhydrohexitol et d'un autre composé dihydroxy aliphatique

Country Status (7)

Country Link
US (1) US20230340190A1 (fr)
EP (1) EP4168469A1 (fr)
JP (1) JP2023529826A (fr)
KR (1) KR20230027030A (fr)
CN (1) CN115667357A (fr)
MX (1) MX2022016129A (fr)
WO (1) WO2021254892A1 (fr)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2438053A1 (de) 1973-08-07 1975-02-20 Teijin Ltd Verfahren zur herstellung aromatischer polyester
JPH04345616A (ja) 1991-05-22 1992-12-01 Nippon G Ii Plast Kk ポリカーボネート、ポリカーボネート組成物およびこれらの製造方法
WO2001032742A1 (fr) 1999-11-01 2001-05-10 General Electric Company Procede de preparation de carbonates de polyester
US20040092703A1 (en) 2002-11-13 2004-05-13 Germroth Ted Calvin Method for making isosorbide containing polyesters
US20090105393A1 (en) 2007-10-18 2009-04-23 Bernardus Johannes Jansen Isosorbide-based polycarbonates, method of making, and articles formed therefrom
JP2010077398A (ja) 2008-08-28 2010-04-08 Teijin Ltd ポリカーボネート樹脂およびその製造方法
EP3026074A1 (fr) 2013-07-24 2016-06-01 SK Chemicals Co., Ltd. Poly(ester de carbonate) hautement résistant à la chaleur et hautement transparent et son procédé de préparation
EP3248999A1 (fr) 2015-01-22 2017-11-29 SK Chemicals Co., Ltd. Nouveau procédé de préparation d'un ester de polycarbonate très transparent et très résistant à la chaleur
WO2019093770A1 (fr) 2017-11-09 2019-05-16 에스케이케미칼 주식회사 Produit moulé fabriqué à partir d'un ester de polycarbonate résistant à la chaleur élevée
WO2019147051A1 (fr) 2018-01-24 2019-08-01 에스케이케미칼 주식회사 Ester de polycarbonate d'origine biologique et son procédé de préparation
WO2020085686A1 (fr) 2018-10-26 2020-04-30 에스케이케미칼 주식회사 Composition polymérisable et ester de copolycarbonate et procédé pour sa production
EP3708601A1 (fr) 2017-11-09 2020-09-16 SK Chemicals, Co., Ltd. Produit moulé fabriqué à partir d'un ester de polycarbonate résistant à la chaleur élevée

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2438053A1 (de) 1973-08-07 1975-02-20 Teijin Ltd Verfahren zur herstellung aromatischer polyester
JPH04345616A (ja) 1991-05-22 1992-12-01 Nippon G Ii Plast Kk ポリカーボネート、ポリカーボネート組成物およびこれらの製造方法
WO2001032742A1 (fr) 1999-11-01 2001-05-10 General Electric Company Procede de preparation de carbonates de polyester
US20040092703A1 (en) 2002-11-13 2004-05-13 Germroth Ted Calvin Method for making isosorbide containing polyesters
US20090105393A1 (en) 2007-10-18 2009-04-23 Bernardus Johannes Jansen Isosorbide-based polycarbonates, method of making, and articles formed therefrom
JP2010077398A (ja) 2008-08-28 2010-04-08 Teijin Ltd ポリカーボネート樹脂およびその製造方法
EP3026074A1 (fr) 2013-07-24 2016-06-01 SK Chemicals Co., Ltd. Poly(ester de carbonate) hautement résistant à la chaleur et hautement transparent et son procédé de préparation
EP3248999A1 (fr) 2015-01-22 2017-11-29 SK Chemicals Co., Ltd. Nouveau procédé de préparation d'un ester de polycarbonate très transparent et très résistant à la chaleur
WO2019093770A1 (fr) 2017-11-09 2019-05-16 에스케이케미칼 주식회사 Produit moulé fabriqué à partir d'un ester de polycarbonate résistant à la chaleur élevée
EP3708601A1 (fr) 2017-11-09 2020-09-16 SK Chemicals, Co., Ltd. Produit moulé fabriqué à partir d'un ester de polycarbonate résistant à la chaleur élevée
WO2019147051A1 (fr) 2018-01-24 2019-08-01 에스케이케미칼 주식회사 Ester de polycarbonate d'origine biologique et son procédé de préparation
WO2020085686A1 (fr) 2018-10-26 2020-04-30 에스케이케미칼 주식회사 Composition polymérisable et ester de copolycarbonate et procédé pour sa production

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CAS, no. 102-09-0
CAS, no. 1122-58-3
KRICHELDORF ET AL., MACROMOL. CHEM. PHYS, vol. 211, 2010, pages 1206 - 1214
OH ET AL., MACROMOLECULES, vol. 46, 2013, pages 2930 - 2940
S. A. PARK ET AL., POLYMER, no. 116, 2017, pages 153 - 159

Also Published As

Publication number Publication date
EP4168469A1 (fr) 2023-04-26
CN115667357A (zh) 2023-01-31
KR20230027030A (ko) 2023-02-27
MX2022016129A (es) 2023-02-09
JP2023529826A (ja) 2023-07-12
US20230340190A1 (en) 2023-10-26

Similar Documents

Publication Publication Date Title
DE2712435C2 (fr)
EP1044093A1 (fr) Utilisation de matieres de moulage en polyester de poids moleculaire eleve
WO2020126806A1 (fr) Carbonates de polyester obtenus à partir de diacides cycloaliphatiques et de diols aliphatiques et leur procédé de production
EP0105399B1 (fr) Compositions de moulage thermoplastiques
DE2113442A1 (de) Verfahren zur Herstellung von Polyestern
WO2021254892A1 (fr) Carbonates de polyester obtenus à partir de diacides cycloaliphatiques, de 1,4 : 3,6-dianhydrohexitol et d'un autre composé dihydroxy aliphatique
EP4168467A1 (fr) Polyestercarbonates à base de diacides cycloaliphatiques, de 1,4 : 3,6-dianhydrohexitol et de quantités spécifiques d'un composé dihydroxy aliphatique supplémentaire
EP4077470B1 (fr) Carbonates de polyester des diacides cycloaliphatiques et des diols aliphatiques et leur procédé de production
EP4168470B1 (fr) Carbonate de polyester à proportion définie dans des groupes ester
WO2021254894A1 (fr) Carbonates de polyester constitués de différents diols dans un rapport défini
EP0054807A2 (fr) Copolyesters thermoplastiques en bloc
EP4077469B1 (fr) Procédé de fabrication d'un carbonate de polyester
EP0054808A1 (fr) Copolyesters thermoplastiques en bloc, procédé pour leur fabrication et leur utilisation pour la fabrication de corps moulés
DE2435507A1 (de) Thermoplastische carbonatmodifizierte copolyester und verfahren zu ihrer herstellung
EP3837237B1 (fr) Procédé de production d'un diester cycloaliphatique
WO2022263319A1 (fr) Oligoesters comprenant du résorcinol et de l'acide iso-et/ou téréphtalique, carbonates de polyester correspondants et leur préparation
EP0543265A1 (fr) Polytéréphtalate d'éthylène modifié et son utilisation pour la fabrication de récipients par extrusion-soufflage
WO2023208897A1 (fr) Mélange de carbonate de polyester et sa production par l'intermédiaire d'un prépolymère de carbonate de polyester
DE2243488A1 (de) Verfahren zur herstellung von thermoplastischen copolyesterformmassen
AT264140B (de) Verfahren zur Herstellung 2,5-Dihydroxyterephthalsäure enthaltender Polyester und Copolyester

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21732030

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022574104

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2021732030

Country of ref document: EP

Effective date: 20230119

NENP Non-entry into the national phase

Ref country code: DE